Structural, theoretical and spectroscopic studies of the dichloride hexahydrate cube [Cl₂(H₂O)6]^2-

Author(s)

James R. Butchard, Owen J. Curnow, David J. Garrett, Robert G. A. R. Maclagan, Eugen Libowitzky, Paula M. B. Piccoli, Arthur J. Schultz

Abstract

The structure of the dichloride hexahydrate cube, [Cl2(H2O)6]2-, as a salt with the tris(diisopropylamino)cyclopropenium cation, [C3(NiPr2)3]+, has been determined by low-temperature X-ray and neutron-diffraction studies. H atoms not involved in O-HCl bonding are disordered over two 0.5 occupancy sites around the O6 ring. Calculations of the dianionic cube in the gas phase show remarkably good agreement with the solid-state structures with the exception of short O-H bond distances around the O6 ring that suggests the involvement of a dynamic process. The cluster was also characterised by single-crystal infrared spectroscopy, and vibrational wavenumbers were found to be in good agreement with hydrogen bonding distances. Dibromide and difluoride hexahydrates were also studied theoretically, and OO distances were found to decrease in the order difluoride > dichloride > dibromide > (H2O)6 and as OOO angles increased towards an almost planar ring in (H2O)6. NMR spectra of a chloroform solution of the hydrated salt at -25 °C is consistent with cluster formation.

Organisation(s)

Department of Mineralogy and Crystallography

External organisation(s)

University of Canterbury, Argonne National Laboratory

Journal

Dalton Transactions

Volume

41

Pages

11765-11775

No. of pages

11

ISSN

1477-9226

Publication date

2012

Peer reviewed

Yes

Austrian Fields of Science 2012

104003 Inorganic chemistry, 105113 Crystallography, 1030 Physics, Astronomy

Portal url

https://ucrisportal.univie.ac.at/en/publications/65b2c996-5e62-4e43-9e0c-2facd71a0937